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Advances in polyaniline-based nanocomposites

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Pratibha Singh at University of Delhi
Pratibha Singh
S. K. Shukla at University of Delhi
S. K. Shukla
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In this review article, synthesis, properties and applications of polyaniline-based nanocomposites (PANI-NCs) have been described. Different methods (viz chemical, electrochemical, photochemical and mechano-chemical) and size confinement tools used for preparation of PANI-NC are described with their advantageous and disadvantageous features. On the basis of synergized electrical, magnetic, optical, mechanical and thermoelectric properties, PANI-NCs are used in development of sensors, support catalysts, water purifications, energy and biomedicals. Further, applications of PANI-NC are elaborated with suitable examples centring on the role of nano-confinements and chemical modification along with existing challenges for commercial uses.
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REVIEW
Advances in polyaniline-based nanocomposites
Pratibha Singh
1,2
and S. K. Shukla
2,
*
1
Department of Chemistry, University of Delhi, New Delhi, Delhi 110007, India
2
Department of Polymer Science, Bhaskaracharya College of Applied Sciences, University of Delhi, New Delhi, Delhi 110075, India
Received: 13 July 2019
Accepted: 16 October 2019
Published online:
30 October 2019
ÓSpringer Science+Business
Media, LLC, part of Springer
Nature 2019
ABSTRACT
In this review article, synthesis, properties and applications of polyaniline-based
nanocomposites (PANI-NCs) have been described. Different methods (viz
chemical, electrochemical, photochemical and mechano-chemical) and size
confinement tools used for preparation of PANI-NC are described with their
advantageous and disadvantageous features. On the basis of synergized elec-
trical, magnetic, optical, mechanical and thermoelectric properties, PANI-NCs
are used in development of sensors, support catalysts, water purifications,
energy and biomedicals. Further, applications of PANI-NC are elaborated with
suitable examples centring on the role of nano-confinements and chemical
modification along with existing challenges for commercial uses.
Introduction
The polymers were known as electrical insulator
before the breakthrough discovery for drastic
increase in conductivity of polyacetylene by chemical
doping of iodine in 1977 by Shirakawa et al. [1]. This
finding initiated tremendous research to develop
different electrically conducting polymers (CPs) such
as polyacetylene, polyaniline, polypyrrole, poly-
phenylene, poly(p-phenylenevinylene) and polythio-
phene as substitute of metal, semiconductor and
insulator [2–6]. However, the basic limitation of CPs
is stability, processability and tuneable electrical and
optical properties. The steps reported to eliminate the
limitations are formation of composites, blends,
doping and size confinements. Currently size con-
finement composite at nanoscale has also boosted up
tremendous application of CP in the field of devices,
energy storage, sensing and water purification. Thus,
wide-range CP-based nano-composite structures
with wide range of morphology like particle, rod,
fibre, micelles and core shell have been prepared
[7–10]. The presence of a chain of conjugated double
bonds in polymeric backbones serves as road map for
electron conduction to explain the electrical conduc-
tivity. In this regard, band engineering and energy
alignment has been pursued a hot topic of research
for designing suitable materials for different devices
[11–15]. Several significant innovations were reported
for application in different devices like sensors, solar
cells, energy devices, catalysts, adsorbent, etc.
Among the different CPs, polyaniline (PANI) has
been used since 1836 as aniline black due to its ease of
synthesis, stability, possibility to control size and
formation of hybrid structure. It is of great interest in
device applications due to stability of doped/un-
doped states, ease of structural modification and
solution processability [16–20]. The trend in
Address correspondence to E-mail: sarojshukla2003@yahoo.co.in
https://doi.org/10.1007/s10853-019-04141-z
J Mater Sci (2020) 55:1331–1365
Review
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
... According to the literature, PANI constitutes a characteristic conjugated polymer possessing prolonged πconjugated esystems and Eg values ranging from 1.8 to 4 eV, depending on its structure, the utilized dopant, as well as the dopant's concentration. Additionally, PANI constitutes an effective edonor and h + transporter under visible-light irradiation [39,[51][52][53][54][55][56][57][58]. ...
... According to the literature, PANI constitutes a characteristic conjugated polymer possessing prolonged π-conjugated e − systems and E g values ranging from 1.8 to 4 eV, depending on its structure, the utilized dopant, as well as the dopant's concentration. Additionally, PANI constitutes an effective e − donor and h + transporter under visible-light irradiation [39,[51][52][53][54][55][56][57][58]. ...
Biocompatible PANI-Encapsulated Chemically Modified Nano-TiO2 Particles for Visible-Light Photocatalytic Applications
Article
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Polyaniline (PANI) constitutes a very propitious conductive polymer utilized in several biomedical, as well as environmental applications, including tissue engineering, catalysis, and photocatalysis, due to its unique properties. In this study, nano-PANI/N-TiO2 and nano-PANI/Ag-TiO2 photocatalytic composites were fabricated via aniline’s oxidative polymerization, while the Ag-and N-chemically modified TiO2 nanopowders were synthesized through the sol–gel approach. All produced materials were fully characterized. Through micro-Raman and FT-IR analysis, the co-existence of PANI and chemically modified TiO2 particles was confirmed, while via XRD analysis the composites’ average crystallite size was determined as ≈20 nm. The semi-crystal structure of polyaniline exhibits higher photocatalytic efficiency compared to that of other less crystalline forms. The spherical-shaped developed materials are innovative, stable (zeta potential in the range from −26 to −37 mV), and cost-effective, characterized by enhanced photocatalytic efficiency under visible light (energy band gaps ≈ 2 eV), and synthesized with relatively simple methods, with the possibility of recycling and reusing them in potential future applications in industry, in wastewater treatment as well as in biomedicine. Thus, the PANI-encapsulated Ag and N chemically modified TiO2 nanocomposites exhibit high degradation efficiency towards Rhodamine B dye upon visible-light irradiation, presenting simultaneously high biocompatibility in different normal cell lines.
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... The constituents can be any type of material including metals/metal oxide, polymers, ceramics, composites, etc. themselves. The properties of composites can be tailored by selecting and combining specific constituents and by controlling the processing conditions during their preparation [125,126]. However, PAni has attractive properties but also shows some limitations, which impact its applications. ...
A review on polyaniline and its composites: from synthesis to properties and progressive applications
Article
Full-text available
  • Apr 2024
  • J MATER SCI
Polyaniline (PAni) is a widely studied conductive polymer that has unique properties such as high conductivity and stability. However, poor solubility and mechanical properties limit its prospective applications. To overcome these limitations, different synthesis methods have been developed and studied. One of these methods is to make the composites of PAni which displayed prominent results not only in addressing poor stability but also in achieving high mechanical properties. This review summarizes various synthesis methods, properties, and applications of PAni composites that have been incorporated with different materials such as carbon, carbon nanotube, graphite, graphene oxide, metal and metal oxides, metal–organic framework, bio-molecules, silica, and many more to enhance their potential applications. The most important applications of the PAni composite are briefly revealed at the end of this review and discussed appropriately.
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... PANI, a conducting polymer, has been employed in different applications such as sensors [14], supportive catalysts [15], water puri cations [16], protection against corrosion in organic coverings [17], electrical appliances [18] and power devices because of its good electrical conductivity, high ecological oxygen moisture absorption and ease of manufacturing [19,20]. In a recent research, PANI is doped with reduced graphene oxide (RGO). ...
CuO/PANI nanocomposites: An efficient catalyst for degradation and reduction of pollutants
Preprint
Full-text available
  • Jan 2024
Textile dyeing releases over 80% of industrial effluents without proper treatment. Dye discharged into effluents typically need degradation before release into aquatic environments. In this regard, the present paper reports the nanocomposite copper oxide/polyaniline (CuO/PANI) is successfully synthesized by in situ chemical oxidative polymerization method and investigate their catalytic activity against organic dyes and nitro-compounds. CuO nanoparticles are synthesized by colloidal sol-gel method using oxalic acid as capping agent to obtained desired morphology. The elemental composition, unit cell and lattice parameters of nanocomposites are characterized by using XRD. The XRD revealed that nanoparticles are extremely crystalline, but nanocomposites are amorphous because of the presence of polymer. The structural and elemental analysis of CuO and CuO/PANI is confirmed by SEM and EDX analysis. FTIR spectra of CuO showed bending vibration while CuO/PANI showed the presence of benzenoid and quinoid rings. Catalytic productivity of the CuO and CuO/PANI as catalysts in degradation of dyes and reduction of nitro-compounds are also studied. The degradation and reduction processes are monitored through the utilization of UV-Vis spectrophotometer. The catalytic activity of both catalysts is evaluated by several parameters including k app , degradation/reduction time, % degradation/reduction, degraded/reduced concentration and half-life. Among all substrates, highest k app is 0.0653 min ⁻¹ for CV by CuO while 0.0502 min ⁻¹ for EBT by CuO/PANI due to large surface area. On degradation or reduction rate of substrates, the impact of functional group type and orientation, bond type and steric hindrance are also investigated.
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... Cao et al., [47] also prepared PANI nano-tubes encapsulated nickel nanowires by using an alumina membrane as a hard template. Similarly, certain inorganic particles were also used as templates like nickel particles for the synthesis of PANI nanofibers, etc., [48]. ...
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... Polymers are considered as versatile materials that are suitable for an uncountable number of applications due to their controllable properties. The low cost of polymers, which can be produced in various forms and properties, makes them indispensable for many fields [19][20][21]. In the detection of volatile organic compounds (VOCs), these unique polymers are utilized in the production of sensitive, fast responding, reversible thin film chemicals sensor elements. ...
Surface plasmon resonance chemical sensor modified with α-naphthylmethacrylate nano thin film for chloroform detection
Article
  • Jan 2023
  • (RESM)
The research on the rapid and sensitive detection of pollution caused by the products and technologies used has recently attracted attention in the literature. In the detection of volatile organic compounds (VOCs), polymers/monomers are used in the production of sensitive, fast-responding, reversible thin-film gas sensor elements. In this work, the monomer α-Naphthylmethacrylate was selected as thin film sensor element. The α-Naphthylmethacrylate-based nano thin films were prepared with technique of LB. Monomer LB thin films fabricated onto gold-coated glass substrate to investigate their vapour sensing properties by using Surface Plasmon Resonance (SPR) optical technique. This prepared monomer-based thin film sensor exposed to five different concentrations of chloroform vapors varying between 13.98x103-69.9x103 ppm and the sensor response values were recorded. Swelling dynamics’ of this monomer thin film sensor was also illuminated by using Fick's early-time diffusion law. Diffusion coefficients of α-Naphthylmethacrylate LB thin film sensor materials exposed to the five different concentrations of chloroform vapor were calculated with the help of reflected light intensity graph data and Fick's Law as a function of time. It was determined that the diffusion coefficient values of the first and second slope regions as varying between 5.72x10-17-21.97x10-17 cm2s-1 and 3.06x10-17-6.25x10-17 cm2s-1, respectively. SPR kinetic measurement results showed that α-Naphthylmethacrylate material is promising for the detection of chloroform vapor.
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Fundamentals and emerging applications of polyaniline
Book
  • Aug 2019
Fundamentals and Emerging Applications of Polyaniline presents in-depth coverage of synthetic routes, characterization tools, experimental procedures, and the preparation of PANI-based materials for advanced applications. Sections examine the various synthetic routes available for the polymerization of aniline, covering both conventional methods and new approaches, specific PANI-based materials, and their potential applications. Users will be able to understand how to use these methods in areas such as electromagnetic interference shielding, rechargeable batteries, light emitting diodes, super capacitors, anti-static packaging and coatings, photonics, biomedical applications, chemical and biochemical sensors. This is a highly valuable source of information for researchers, scientists and graduate students in polymer science, polymer composites, polymer chemistry, nanotechnology, physics and materials science. Covers the latest synthetic approaches, such as ultrasound-assisted polymerization, irradiation path and electrochemical polymerization Offers detailed information on PANI-based composites, including graphene, CNT and functionalized polyaniline Explains how different PANI-based materials can be geared for specific cutting-edge applications across a range of fields
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High Performance Competence of Polyaniline-based Nanomaterials
Article
  • Jun 2019
  • MATER RES INNOV
Polyaniline (PANI) is one of the important types of intrinsically conducting polymers. Processability of PANI is daunting due to high level of conjugation and rigid backbone. PANI-based nanomaterials have been identified as new materials for rapidly growing technologies. Owing to enhanced and exceptional nanostructural characteristics, PANI-based nanomaterials have gained research curiosity. Thus, challenges faced in processing of neat PANI have led to the growth of PANI-based nanomaterials. This article presents development of PANI-based nanomaterials, their potential prospects in various technological fields, and future direction. Potential of PANI-based nanomaterials has been analysed in membranes, anticorrosion, solar cell, supercapacitor, sensor, and biomedical.
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Preparation and performance of PANI-TiO2 nanotube arrays composite electrode by in-situ microcavity polymerization
Article
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  • MATER CHEM PHYS
TiO2 nanotube arrays (TNTA) were firstly impregnated with ethanol solution containing aniline monomer, then the polyaniline-TiO2 nanotube arrays (PANI-TNTA) composite electrode was prepared through polymerization of aniline monomer in the microcavity of the nanotubes using ammonium persulfate (APS) as the initiator. The effects of aniline and APS concentration on the properties of the composite electrodes were studied. The electrochemical performances of the composite electrode in sodium sulfate aqueous solution and sulfuric acid aqueous solution were compared at different potential windows of −0.2–1 V and −0.2–1.8 V. Results show that the composite electrode exhibits optimal performance when the concentration of aniline and APS is 0.2 M and 0.05 M, respectively. The composite electrode has fair good electrochemical performances under various testing conditions especially in sulfuric acid aqueous solution, it has a maximum capacitance of 816.7 F g⁻¹, and at the enlarged potential window of −0.2–1.8 V, its energy densities are higher than those of −0.2–1 V. The composite electrode also has excellent rate and cycling properties.
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Progress in Conductive Polyaniline-Based Nanocomposites for Biomedical Applications: A Review
Article
  • Sep 2019
Inherently conducting polymers (ICPs) are a specific category of synthetic polymers with distinctive electro-optic properties, which involve conjugated chains with alternating single and double bonds. Polyaniline (PANI), as one of the most well-known ICPs, has outstanding potential applications in biomedicine because of its high electrical conductivity and biocompatibility caused by its hydrophilic nature, low-toxicity, good environmental stability and nanostructured morphology. Some of the limitations in the use of PANI, such as its low processability and degradability, can be overcome by the preparation of its blends and nanocomposites with various (bio)polymers and nanomaterials, respectively. This review describes the state-of-the-art of biological activities and applications of conductive PANI-based nanocomposites in the biomedical fields, such as antimicrobial therapy, drug delivery, biosensors, nerve regeneration and tissue engineering. The latest progresses in the biomedical applications of PANI-based nanocomposites are reviewed to provide a background for future research.
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Quantum dots of molybdenum nitride embedded in continuously distributed polyaniline as novel electrode material for supercapacitor
Article
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Molybdenum nitride (Mo2N) and molybdenum nitride/polyaniline composites (Mo2[email protected]) have been prepared by simple static precipitation and in situ growth methods. The morphological and structural properties and chemical composition of the prepared materials have been analyzed by transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The obtained results illustrate that in molybdenum nitride/polyaniline composites, polyaniline has been allocate continuously embedded with the quantum dots of molybdenum. Therefore, the formation of quantum dots of molybdenum and its uniform distribution in polyaniline bulk suggested that the synthesized materials could be used as an electrode material of supercapacitors. From the results of electrochemical analysis, the mass ratio capacitance of molybdenum nitride/polyaniline composites have been found to be 111.8 F/g at 0.5 A/g, while the mass ratio capacitance of pure molybdenum nitride is only 47.5 F/g at the same current density. Hence, obtained results clearly confirm that molybdenum nitride/polyaniline composites nanostructured quantum dot material is one of the best and novel electrode materials for high performed supercapacitors which exhibits excellent electrochemical properties.
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Polyaniline@porous polypropylene for efficient separation of acid by diffusion dialysis
Article
  • Aug 2019
  • SEP PURIF TECHNOL
Herein we have discussed the robust design and synthetic methodology of polyaniline based exceptional chemical and mechanical stable composite membrane for acid recovery by diffusion dialysis. Physicochemical characterization of the membrane was carried out to find its hydrophilic/hydrophobic characteristic and its effect on separation of HCl and H2SO4 from the simulated solution. The high retention of sulfuric acid or high permeation of HCl was explained on the basis of Gibbs free energy of hydration of Cl⁻ and SO4²⁻ ions. The obtained diffusion coefficient (UH⁺) for PANI and A-PANI membrane was in the range of 0.013–0.042 m h⁻¹ for HCl, H2SO4 and effluent solution. The maximum acid recovery was 43% for A-PANI and 32% for PANI. The acid recovery for locally available effluent solution was ∼34% indicating potential use of synthesized membranes in acid recovery by diffusion dialysis.
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Multilayer-Structured Ni-Co-Fe-P/Polyaniline/Polyimide Composite Fabric for Robust Electromagnetic Shielding with Low Reflection Characteristic
Article
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  • CHEM ENG J
Fabrication of highly efficient electromagnetic shielding materials with low reflection and strong absorption characteristics is important to address the ever growing electromagnetic wave problem. Here, a facile and reliable strategy is proposed to prepare multilayer-structured nickel-cobalt-ferrum-phosphorus/polyaniline/polyimide (Ni-Co-Fe-P/PANI/PI) fabrics via a successive step of in-situ polymerization and electroless plating. By controlling the composition of Ni-Co-Fe-P alloy judiciously, the dielectric-magnetic loss characteristics of Ni-Co-Fe-P/PANI/PI fabrics can be balanced, especially the 50Ni-Co-Fe-P/PANI/PI (CNi²⁺:CCo²⁺:CFe²⁺=2:1:1) fabric, displaying the highest electromagnetic shielding effectiveness (40.5–69.4 dB) at X-band frequency range, which is superior to those of traditional metallic fabrics as well as carbon materials or conductive polymers coated fabrics with only 0.2 mm thickness. The proper impedance matching characteristic ensures that most of incident electromagnetic waves are penetrated into material rather than directly reflected back. The residual electromagnetic waves are dissipated through the dielectric-magnetic loss synergistic effect from PANI and Ni-Co-Fe-P layer. In addition, the advantageous features in practical application properties allow for robust and stable electromagnetic shielding efficiency and harsh environments resistent.
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Effective removal of mercury, arsenic and lead from aqueous media using Polyaniline-Fe3O4- silver diethyldithiocarbamate nanostructures
Article
  • Aug 2019
  • J CLEAN PROD
In today's world, millions of people are under harmful influences of severely toxic elements (i.e. Hg, As and Pb), all of which lead to irreversible damages to nature and living species' health; thereby its barebone essential to removal these wastes from the ecosystem. Herein, we proposed a highly complex, porous, anti-bacteria, anti-fungal and interconnected sulfur-rich nanostructure based on polyaniline-Fe3O4-silver diethyldithiocarbamate (PANI-F-S) which can remove Hg, As and Pb from aqueous media of about 99% at optimum conditions. Likewise, outcome of Langmiur isotherm showed qm values of about 222.2, 175.4 and 40.3 mg g−1 for Hg, As and Pb absorption onto the PANI-F-S, respectively, which show the highest absorption rate ever achieved for Hg and As at low concentrations within the range of ng or μg. Likewise, outcome of Pesudo-second-order kinetic which showed the highest compatibility with experimental data, revealed qe,exp/qe, cal for Hg, As and Pb about 157.4/163.9, 132.9/138.88 and 108.3/111.1 mg g−1 at concentration of 45 μg mL−1, respectively. The outcome of this study showed that PANI-F-S can efficiently remove Hg, As and Pb from aqueous media and completely eliminate selected gram positive/gram negative bacteria and yeast at 1 mg mL−1 concentration which is vital for reaching the drinking water standard and removing the threat from millions of people worldwide.
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A Review on Polyaniline-based Materials Applications in Heavy Metals Removal and Catalytic Processes
Article
  • Aug 2019
  • SEP PURIF TECHNOL
Adsorption and catalytic applications of polyaniline-based materials have witnessed an increasing rate in recent years. Polyaniline (PAn), an important member of conductive polymers, is known for its high conductivity, simple preparation, and reasonable stability. In terms of adsorption perspective, novel PAn-based polymeric composites and nanocomposites have been developed to address the issue of growing scale of water contamination by different mono- and multivalent heavy metal ions in recent years. Owing to its distinct features such as ease of production and biocompatibility, PAn can be combined with a wide range of organic/inorganic, natural or synthetic materials to procure novel sorbents with higher removal efficiency and improved sorption properties for heavy metal ions. Applications of PAn-based materials for removal of other pollutants from aqueous media are briefly presented as well. Having said that PAn is a stable material, PAn-derived materials have also exhibitied good recyclability which is a crucial feature in the adsorption process. In terms of catalysis perspective, PAn can also be counted as a catalytic species or as a material for holding or protecting precious catalytic components. Either acting as a protective material or as a catalytic component, PAn has proven its capability as a proper platform for heterogenizing the catalyst of many catalytic reactions. Herein, a concise review of both adsorptive and catalytic behavior of new materials derived from polyaniline is presented. The attention was directed to the preparation protocles of PAn-derived materials along with the role of PAn in the related applications. Furthermore, other potential applications of PAn-based materials are also briefly summarized.
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